Effect of Vibronic Coupling on Correlated Triplet Pair Formation in the Singlet Fission Process of Linked Tetracene Dimers

Tetracene-based singlet fission (SF) materials show application prospects as triplet sensitizers in organic optoelectronics. SF involves internal conversion from photoexcited singlet states 1 (S 1 S 0 ) to correlated triplet pair states 1 (T 1 T 1 ). We derive an expression for the internal conversion rate on the basis of the Fermi golden rule with an artificial Lorentzian broadening. The internal conversion rate depends on the interstate vibronic couplings (VCs) and energy difference (Δ E SF ) between 1 (S 1 S 0 ) and 1 (T 1 T 1 ). Therefore, understanding the interplay between interstate VCs and Δ E SF is necessary to reveal how the structure–property relationship affects the SF efficiency. Here, we propose a method to quantitatively analyze interstate VCs between 1 (S 1 S 0 ) and 1 (T 1 T 1 ). We apply this method to SF in ortho -, meta -, and para -bis(ethynyltetracenyl)benzene and identify an effect of interstate VCs on the 1 (T 1 T 1 ) formation rate. The interstate VCs of the meta dimer are remarkably weak, which reasonably explains the experimentally obtained slow 1 (T 1 T 1 ) formation rate. The weak VCs result from a very small overlap density between 1 (S 1 S 0 ) and 1 (T 1 T 1 ) of the meta dimer. Furthermore, we investigate structure-dependence of the 1 (T 1 T 1 ) formation rate of the para dimer and find that the para dimer shows large VCs and small Δ E SF when the rotational angle between the two tetracene units is large, which leads to the faster 1 (T 1 T 1 ) formation rate than those of the ortho and meta dimers. The rotation of the tetracene units is the origin of the experimentally observed fast 1 (T 1 T 1 ) formation rate of the para dimer.